CN110511257A - A kind of preparation method of four-O- acetyl group -2- phthaloyl imino-beta- glucose - Google Patents

A kind of preparation method of four-O- acetyl group -2- phthaloyl imino-beta- glucose Download PDF

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Publication number
CN110511257A
CN110511257A CN201910896621.5A CN201910896621A CN110511257A CN 110511257 A CN110511257 A CN 110511257A CN 201910896621 A CN201910896621 A CN 201910896621A CN 110511257 A CN110511257 A CN 110511257A
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China
Prior art keywords
glucose
acetyl group
beta
phthaloyl imino
alpha
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CN201910896621.5A
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CN110511257B (en
Inventor
李文举
高健
庄永忠
唐鹏飞
李秀珍
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Ji'nan Biological Medicine Technology Co Ltd
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Ji'nan Biological Medicine Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
    • C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
    • C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
    • C07H19/044—Pyrrole radicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The present invention provides a kind of synthetic methods of four-O- acetyl group -2- phthaloyl imino-beta- glucose; using four-O- acetyl group -2- phthaloyl imino-alpha- glucose as starting material; raw material is easy to get, is at low cost; 1- isomerization generate four-O- acetyl group -2- phthaloyl imino-beta- glucose under the action of acetic acid, acetic anhydride and catalytic amount trifluoromethanesulfonic acid scandium and previous methods relatively considerably reduce the production cost of the important intermediate.This technology process conditions are mild, product separation is easy, high income, are conducive to the industrialization of four-O- acetyl group -2- phthaloyl imino-alpha- glucose preparation, to promote the exploitation and production of medicine series and functional product downstream.

Description

A kind of preparation of four-O- acetyl group -2- phthaloyl imino-beta- glucose Method
Technical field
The invention belongs to carbohydrate chemistries to synthesize field, and in particular to a kind of four-O- acetyl group -2- phthaloyl iminos - Beta- glucose preparation method.
Background technique
Four-O- acetyl group -2- phthaloyl imino-beta- glucose (I) are a kind of sugar synthesis for having extensive use Building block can derive the functional compounds of a variety of important uses, such as cardiovascular medicament Huang reaches the synthesis of liver certain herbaceous plants with big flowers sodium.But Its 1- alpha isomers (II) is always easy as by-product to generate in traditional preparation process, by way of crystallization It is difficult to remove, needs to be isolated and purified with silicagel column:
。
The position the 1- alpha acetyl group reactivity of isomers can not show a candle to beta configuration, therefore the beta for preparing high-purity is different Structure body is to prepare the building block problem to be solved.1- alpha isomers at present can be big with easy method Amount prepares (A Facile and Stereoselective Synthesis of 3,4,6-Tri-O-Acetyl-2-Deoxy- 2-Phthalimido-β-D-Glucopyranosyl ChlorideJournal of Chemical Research, 2013, 37,467-469), cost price is far below beta isomers.
The existing pure beta configuration of synthesis is with four-O- acetyl group -2- amino-without the method for using silica gel post separation Beta- glucosamine salt hydrochlorate is raw material (A Fluorescent Transport Assay Enables Studying AmpG Permeases Involved in Peptidoglycan Recycling and Antibiotic Resistance, ACS Chemical Biology, 2016,2626-2635), but the cost of material of this method is high, it is difficult to a large amount of low cost manufacturings Target product:
。
Summary of the invention
For in current four-O- acetyl group -2- phthaloyl imino-beta- glucose preparation process it is at high cost and The problems such as containing isomers, the present invention provides a kind of four-O- acetyl group -2- phthaloyl imino-beta- glucose systems Preparation Method, high income, at low cost, product purity height, suitable for industrialized production.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of synthetic method of four-O- acetyl group -2- phthaloyl imino-beta- glucose, including following step It is rapid:
Under the catalysis of trifluoromethanesulfonic acid scandium, four-O- acetyl group -2- phthaloyl imino-alpha- glucose in acetic acid and The in the mixed solvent normal-temperature reaction of acetic anhydride, reaction solution obtains four-O- acetyl group -2- phthalyl of product after isolating and purifying sub- Amino-beta- glucose.
Preferably, the volume ratio of acetic acid and acetic anhydride is 1:1.
The product isolates and purifies mode are as follows: reaction solution is poured slowly into ice water and stirs, and filter cake is drenched with methanol after filtering It washes 3-5 times.
Synthetic route is as follows:
。
The invention has the following advantages that
The present invention using four-O- acetyl group -2- phthaloyl imino-alpha- glucose as starting material, raw material is easy to get, at This is low, and 1- isomerization generate four-O- acetyl group -2- under the action of acetic acid, acetic anhydride and catalytic amount trifluoromethanesulfonic acid scandium Phthaloyl imino-beta- glucose and previous methods relatively considerably reduce being produced into for the important intermediate This.This technology process conditions are mild, product separation is easy, high income, are conducive to four-O- acetyl group -2- O-phthalic imides The industrialization of base-alpha- glucose preparation, to promote the exploitation and production of medicine series and functional product downstream.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited by the following examples.
Embodiment 1
(1) stirring is lower is added the powdered four-O- acetyl group -2- neighbour of 1000g toward the in the mixed solvent of 2L glacial acetic acid and 2L acetic anhydride 0.5g trifluoromethanesulfonic acid scandium is added in phthalimido-alpha- glucose (HPLC purity 98.0%) until completely dissolved, It is stirred to react, is detected through HPLC at room temperature, raw material is fully converted to four-O- acetyl group -2- phthalyl of target product after 12h Imino group-beta- glucose；
(2) system in previous step after reaction is poured slowly into the ice water (0 DEG C) being vigorously stirred, target product analysis Out, it filters, filter cake is eluted 3 times, dried product exhibited 950g with methanol, and yield 96.2%, product is detected through HPLC, and purity is 99.2%。

Claims (3)

1. the synthetic method of four-O- acetyl group -2- phthaloyl imino-beta- glucose of one kind, which is characterized in that packet Include following steps:
Under the catalysis of trifluoromethanesulfonic acid scandium, four-O- acetyl group -2- phthaloyl imino-alpha- glucose in acetic acid and The in the mixed solvent normal-temperature reaction of acetic anhydride, reaction solution obtains four-O- acetyl group -2- phthalyl of product after isolating and purifying sub- Amino-beta- glucose.
2. synthetic method according to claim 1, which is characterized in that the volume ratio of acetic acid and acetic anhydride is 1:1.
3. synthetic method according to claim 1, which is characterized in that the product isolates and purifies mode are as follows: reaction solution It is poured slowly into ice water and stirs, filter cake is eluted 3-5 times with methanol after filtering.
CN201910896621.5A 2019-09-23 2019-09-23 Preparation method of tetra-O-acetyl-2-phthalimido-beta-glucose Active CN110511257B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656868A (en) * 1992-08-07 1994-03-01 Asahi Chem Ind Co Ltd New glycosylation process
WO2012145626A1 (en) * 2011-04-22 2012-10-26 Ancora Pharmaceuticals Inc. Synthetic oligosaccharides for staphylococcus vaccine
US20140170151A1 (en) * 2010-04-23 2014-06-19 A. Stewart Campbell Synthetic Oligosaccharides for Staphylococcus Vaccine
JP2015168625A (en) * 2014-03-05 2015-09-28 株式会社ツムラ Method of producing 4'-o-glucosyl-5-o-methylvisamminol
CN106397500A (en) * 2016-09-12 2017-02-15 济南山目生物医药科技有限公司 Synthetic method of L-glucose
CN106496288A (en) * 2016-09-12 2017-03-15 济南山目生物医药科技有限公司 A kind of preparation method of 2 deoxidation D glucose
CN107629095A (en) * 2017-09-29 2018-01-26 江西科技师范大学 The full acetyl sugar end position selectivity deprotection method of trifluoromethanesulfonic acid hafnium catalysis

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656868A (en) * 1992-08-07 1994-03-01 Asahi Chem Ind Co Ltd New glycosylation process
US20140170151A1 (en) * 2010-04-23 2014-06-19 A. Stewart Campbell Synthetic Oligosaccharides for Staphylococcus Vaccine
WO2012145626A1 (en) * 2011-04-22 2012-10-26 Ancora Pharmaceuticals Inc. Synthetic oligosaccharides for staphylococcus vaccine
JP2015168625A (en) * 2014-03-05 2015-09-28 株式会社ツムラ Method of producing 4'-o-glucosyl-5-o-methylvisamminol
CN106397500A (en) * 2016-09-12 2017-02-15 济南山目生物医药科技有限公司 Synthetic method of L-glucose
CN106496288A (en) * 2016-09-12 2017-03-15 济南山目生物医药科技有限公司 A kind of preparation method of 2 deoxidation D glucose
CN107629095A (en) * 2017-09-29 2018-01-26 江西科技师范大学 The full acetyl sugar end position selectivity deprotection method of trifluoromethanesulfonic acid hafnium catalysis

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MOHAMMADREZA NASIRI等: "Enhanced Mechanical and Adhesion Properties in Sustainable Triblock Copolymers via Non-covalent Interactions", 《MACROMOLECULES》 *
MOHAMMADREZA NASIRI等: "Enhanced Mechanical and Adhesion Properties in Sustainable Triblock Copolymers via Non-covalent Interactions", 《MACROMOLECULES》, 19 March 2018 (2018-03-19), pages 2456 - 2465 *

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